Thenoylaminoanthraquinones



Patented Apr. 25, 1950 ore-Ice "@HENOYLALHNOANTHRAQUINON'ES *HenryRN-Lee-Bitman, and Clarence F. Bel'cher,

Bridgetom'N. 1L, assignors to E. I; du Pont de iNemours & Company,Wilmington,'Del.,a cor- I poration-o'fDelaware iNosnrawingrApplication-Decemberfi, 194 7,,

SeriaLNo. 790,012

5 Claims. (GLEN- 329 This invention, relates ito 'the:..preparation ofdyes and dye intermediatesvoflthetanthraqulnone series, and. more,particularly- Ltoi the production of new thenoylaminoanthraquinonecompounds.

,It is; known. that, by ltherfintroductionao'f benzoylamino groups.inythe arithraquinone molecule, valuable. dyes. of ,varyingshadesas,well as numerous dye lintermediateswhioh are useful in thepreparatlonof dyes may be, produced. These intermediates are valuable .inv thepreparation of vat dyes, .azcid .wool dyes. anddyes for syntheticfibers. V

It is an object .ofthetpresent invention t'oprovide a newand valuableseries of .thenoylaminoanthraqulnone compounds which. are useful. as.dyes for various fibers and'as. intermediates "for thepreparationofother dyes,

We have found that anew and valuablexclass of dyes and dyeintermediatesxmayjbe,produced by condensing aminoanthraquinone compoundswith 2-thenoic acid or its derivatives, whereby compounds of the generalformula:

are produced; in which: n :stands for one otthe numbers 1' or ,2, Xstands Yfor. hydrogen, a, halogen-, methylor nitro-group and wherein Aqstands. for van .vanthraquinoneunucleusv which may contain one or moresimple monovalent con- These thenoylaniinoanthraquinone compounds areproduced by reactin amino'anthraquinones, which may also carryother-simple monovalent substituents, with 2-thenoic acid or itsderivatives by the usual acylating methods.

The following examples are given-to illustrate the invention, it beingunderstood'that'these examples are merely' illustrative and are notto"b'e construed as limitations uponthe'invention. The parts used, unlessotherwise specified, are by weight.

Example 1 .-A mixture of 12,parts of-l-aminoanthraquinone and 84 partsof nitrobenzene is heated to 125 C. under agitation, and then a solution01 L118 parts of Z-thenoyl chloride iii--12 parts of nitrobenzene :isadded dropwise over one-half hour. The charge is heated :at 1=25-135 C.for one hour, cooled to :room-temperatureand filtered. The cake,composed of small, reddishyellow needles, is washed with nitrobenze'ne,alcohol and water, and then dried. The 1-:(2- thenoylamino)anthraquinoneobtained "has a melting point of 282 C. and an analysis of 4.26%nitrogen and 955 sulfur.

The Z-thenoyl ch1oridemay be condensedwith other aminoan'thraquinones by"the samefjgenral method. I lustrative aminoanthraquinone compoundswhich maybe employed, and "the products obtained therefrom, are given inthe following table. 7

, 7 l 1 Product '1 tReactantmg nos nthraqulncnaz i 0 Va we Y NameAppearance gg g i g gg Y I a l-Amlno-4echlm:oanthraquincne1-Chloro;41(2-thenoylamino) anthi-aquinone. Yellow needles '269L5'to'274n" I b l-Aminorbrchloroanthtaqulnone ,L-Qhloro;5;(2thenoylamin0)anthraquinona do 250 to 2540. e r. c l-Aminmil-chloroenthraqflinone1-(2-thenoylamino)-6-ohloroanthraquinone ,do 247 3.7 I d1-Amino-8-chloroanthraquinone .1-.Chloro 8=.(2-thnoylamino)anthraquinoneh '-Greenisbyelldw needles. 231.5 gfiigbfbl'a 0"- I el-Amino-2-methyl-4abromoanr l.lflmthenoylamino)-'2-methyl4-hmm0211-:Yellow needleaecofl -2l7 to 221; 3;29 %-Na thraquin'one. thraquinone.18.87%Bn stituents of the-group consisting: of. -01; -'-:Br. ,v FumbleCH3, --'N02, --NHz, -OH antl "0CH3.. The introductionofthefithenoylamino-tgmup :intorthe .anthraquinone molecule produces,compounds which have unusual, andaunexnected oolor prop- :erties' as:comparecl ito thezconrespontdmglbenzoylr ,amlnoanthraquinone; nompnundm,Even. :im the -simplestianthraquin0ne derivatives the'introduoa tionofxthenoylamina group;.-produoes: oompounds which are deeperinsnadelandiwhicn are stronger on anequal weightbaslsxithanztheveorrespouding ibenzoylamino derivatives.

To a mixture-of 120 :parlts of:mtrobenzene-and 15 parts of leuco1,4-diaminoanthraquinone under agitation at room temperature, 24 partsof 2- thenoylrohloride-are added at once. The-charge .ls vheated to -C.and held for one :houn It is thencooled to room temperature, filtered--.an'd

thecake iswashedwith nitrobenzeneand-alcohol. The; red-orangecrystalline pro'duct is 'slurried ln 5070 ,partsr'or 1sodiumcarbonatesolutionat 80? 'todfli irforeneahalfihjour,rfilteredgwashed alkalis- Example 3 A mxture of 200 partsof nitrobenzene and 25 parts of 1,5-diaminoanthraquinone is heated to150 C., after which 37 parts-of 2-thenoyl chloride are dropped in overone-half hour. The charge is agitated at that temperature for one hour,

cooled to room temperature, filtered, and the cake is washed withnitrobenzene and alcohol. The 1,5-di-( 2-thenoylamino) anthraquinone,which is a yellow-brown needle-like product, is slurried in water,filtered, washed and dried. It dyes vegetablefibers orange-yellow shadesfrom an alkaline-hydrosulfite vat.

Example 4 A mixture of 50 parts of ortho diehlorobenzene, 10 parts of5-chloro-2-thenoic acid and'11.5 parts ofLthionyl chloride is heated at'70-80 C. for 2 hours. then aeratedat that temperature for onehalf hourto removeexcess thionyl chloride. To this solution, 40 parts ofortho-dichlorobenzene and 6 parts of 1,5-diaminoanthraquinone are added.The charge isheated at 150 C. for two hours, stirred until cool andfiltered. The 1,5- di- (5 chloro 2 thenoylamino) anthraquinone, which isin the form of yellow-brown needles. is washed withortho-dichlorobenzene. alcohol. slurried in water, filtered, washed withwater and dried. It has a melting point of 373 C. and an analysis of5.49% nitrogen and 12.8% chlorine. Other 2-thenoic acid derivatives maybe rehours. The charge is cooled and filtered. The2,6di-(2-thenoylamino) anthraquinone, which is a yellow-browncrystalline product, is washed with nitrobenz'ene, alcohol, water anddried. It hasa melting point of 375 C. and a nitrogen content of 6.04%.

When treated in a similar manner 1,5-dichloro- 2,6 diaminoanthraquinonewith 2-thenoyl chloride yields l,5-dichloro-2,6-di(2-thenoylamino)anthraquinone, which forms greenish-yellow cryS- tals.

.With'5-chloro-2-thenoic acid, 1,5-dichloro-2,6- diaminoanthraquinoneyields 1,5 dichloro 2,6- di.(5 chloro 2 -'thenoylamino)anthraquinonewhich likewise forms greenish-yellow crystals.

Example 6 A mixture of '75 parts of ortho-dichlorobenzene, 19 parts of5-chloro-'2+theno ic acid-and'20.8 parts of thionyl chloride'is refluxedone and one-half to two hours, and the solution is aerated onehalf hourat C. to remove excess thionyl chloride. This solution .is cooled toroom temperature and 24.5 parts of 1-amino-5-chloroanthraquinone areadded. The charge is heated at to C. for one hour, cooled, filtered, andthe 1 chloro 5 (5 chloro 2 thenoylamino) anthraquinone, which iscomposed of small greenish-yellow needles, is washedwithorthodichlorobenzene, alcohol, water anddried. It has a meltingpoint of 245 C., a nitrogen content of 3.47% and a chlorine content of17.5%.

Other 2-thenoic acid derivatives may be condensed with1-amino-5-chloroanthraquinone by the same general method. Illustrativereactants and'the products resulting therefrom are shown in thefollowing table.

Product 2-Thenoic Acid Derivative Name Appearance ga g g Analysis O'. a5-B omo-2-thenoic acld..- lC-hlore-5-(li-bromo-z-thenoylaminoienthraquinnne Red yellow needles V 240 l7.22%- Br, 5-Methyl-2-thenolcacid.-. l-Chloro-5-(5-methyl-2-thenoylamino) anthraquiYellow-green'needles.. 248.5 b6Z /SC1 none .-g ,c 5-Nitro-2-thenoic acidl-Chlorafi-(E-nitro-Z-thenoylamino) anthraquinona. Orange-yellowneedles... 263 1%) I acted with 1,5-diaminoanthraquinon using theExample same general procedure. Illustrative reactants and the resultingproducts are given in the following table.

A mixture of 225 parts of nitrobenzene, 25 parts ofleuco-1,4-diaminoanthraquinone and 1 part Product 2-Thenoic AcidDerivative I v Name Appearance @2 22 Analysis O l 0-. 5-Bromo2-thenolcacid l.5-di-(5-brorno-2thenoylamino) anthraqni- Yellow-brown 3574.45%-N,

none

b 5-Methyl-2'thenoic acid 0.. l, 5-di-(5-methyl-2-thenoylamino)anthraqui- Red-brown needles 399 5.82%N none 12.28%S

These products dye vegetable fibers in orangeyellow to very red-yellowshades from bluishcolored alkaline hydrosulfite vats.

Example 5 f Y A mixture'of 25 parts of 2,6- diaminoanthraquinone and 200parts 'of nitrobenzene is heated to C. A solution of 3'7 part'siof2-thenoyl chloride in 25 parts of nitrobenzene is added dropwise overone-half hour, and'the mixture is stirred one hour at 150 C. Thetemperature is then raised to C. and maintained for one and one-halfvioleiicqlor needlesi iswasneu a igeiirree are? dried! Itha'sauii'eltitig en orcer-asses:and r-nitrogencontentor 8f01%".

Example 8; ggriiixture of I50'parts 'of' nitrolie'rizeiie'i-l2 parts o'f'sb'da ash and ';1.2='parts o'f ciiprdus clilorid'is heated tofl'itlunfit all water is an: e11ee;= rea which rmparts of; paratoluene sul'foilamide; is" added *and th'e mixture-surnames smooth. Thetemperature is raised to l80 cf-and 30 'partsof 1-ch1oro-5-(2-thenoylamino) anthraquinone are added over two. hours. Thetemperature is maintained at 200-205" fordhours ahd then lowered to from90 to 100 C. Afterthe addition (if Ell-parts dfialbdhbl-tcitliifiwulitheliiixtiire; it

i's' coole d and filtered at frdm m te-co o. The

c'ak l washed with small quantities or: riltro ben'zene and alcoholanemia-11y freedi from"- solveer by steam distillationi" The allow-browncrystalline prpduct is filt'ered washed-ama-ii-iree and dried.To-350"-pa rts of-96 s ulfuric*acidat-- 1 0 1 2 Ca; 35' party of' the 1dried l -(z-thenoylammo 5-paratoluene sulfamin' anthraquinone are addedslowly and the miritiire' agitated-at 12 6." for t'v'vo'hour's''Thetemperature" is allowed to rise gradually to 18-20 Gandhi-aim tainedovernight-e The solution is drowned in llfifl pa'r'ts' of lee-ariaweterat 5 C. The precipitate is filtered, washed acid-free, slurried in 900parts of'0.'5%" soda ash for two. hours and thenarefiltered'. The Iaaminoa 5:,- (2rj-thenoylamino) anthraquinone, which is". amredeorange;crystallineqproduct; is" washed alkali free and dried. It has a meltingpoint or 282* c. and a nitrogen content of 7.91%.

r yarory iis di (2 j-- theno'ylairl inoiantliradiiifidne is" w as'hedwith "ortho dichlorob enzefie slurri e'df-iii 1 par't's Qf'niethy'lalcohol and filtered. It washed with" methyl alcohoL; washed alk'alifiee with water; seamen dried; It dyes vegetable fibers"- in" blueshades fr0m-an alkaline hydro sulfite vat.

' Emampzeqi mixture ol 15 pa'rt s of. 1 ,-amin0-4-niti0an-.tliraqu-inone 120 parts of dry nitrobenzene and;- 9. 8-- parts o fa2'-then'oy1 chloride is heated at ra -14.5% c. for two hours. It iscooled-and filtered; and-. the yellow-brown crystalline product" is washed w-ith nitrobenzene, alcohol, water; and dried. The resulting 1-nitro-4- (2-.thenoyl' aminolanthraquirione has a melting range of 309-31'1Cpl, a nitrogen content of 7.32%..and a sulfur content'of 8.3

Example 12 K A; mixture or? 120., parts of ortho dichlor'oE- benzeneand, 12 parts; of 1-amino-4-hydroxy -5E chloroanthraquinohe is heated to125 C: and a, solution or 8.7 p'artsor z-thenoyl chloridein 12' parts ofortho-dichlorobenzerie' is then added over onehalf hour; Themixture isheated'one hourl' at BIT-135", C., after which 12 parts of soda ash areadded andthe' temperaturera'lsed td.17 5ffl80? o. A total of" 21 arts ofmethyl pla'lfatoluene, sulfonate are] dropped" in. p'orticq'n"; wisearena period 'of' re hours at" 17521 81) 01, at whichtiriie the reactioni's'complete. The charge isicooledt'o room temperature and filtered Thecake, QOl'llDOSed offvery lon'g' red-orange needles;

isflwashed with ortho-diclilorobenzene-and alco- 1101 and; dried; The,1resulting" l-( 2-the'no'yl amino) -4-m'et'h'o'iy-'5=-chloroanthraquihonehas a melting point o f 28'7.5 C., anitrogencontent of 3:50%' and a chlorine content" of =8i8%;

Other 2-thenoic acid derivatives-of l-amind 'imethoxy-5-chloroanthraquinone that have been prepared are included inthe following table:

Product- Melting Appearance Point Analysis-Found:0alculated5-Chloro-2-thenoic acid 5-Methyl-2-thenoic acid l-[5-Methyl-2thenoylaminol-4-methoxy-5-chloroanthraquinone.

Brownish-orange 250 252 Percent Cl:=l6.40; 16.45.

needles. Percent N2=3.02; 3.24.

Percent S=6.98; 7.4.

Reddish-orange 243-245 Percent C11=8.84; 8.62.

needles. Percent N:=3.90; 3.40.

Percent S=7.58; 7.77.

ride was added over one hour. The charge is held one hour longer at150-155 C., cooled to 70 C. and filtered. The product is washed with 120parts of warm nitrobenzene and with alcohol. It is slurried in 100 partsof hot alcohol, filtered, washed with hot water and dried. The resulting1-hydroxy-4- (2-thenoylamino) anthraquinone has a melting point of285286.5 C.

and a nitrogen content of 3.94%.

Example 10 A mixture of 25 parts of4,8-diamino-L5-dihydroxyanthraquinone and 3'75 parts oforthodichlorobenzene is heated to 90-100 C. and 29 Other compounds ofthis type which may be prepared by the processes as above illustratedare 1-(2 thenoylamino)-2 methylanthraquinone, 1-(5-chloro-2-thenoylamino) -2-methylanthraquinone, 1-(2-thenoylamino) 2methyl-5- aminoanthraquinone, 1 (2 thenoylamino) -2- methyl 6aminoanthraquinone, 1-(2-thenoylamino) -5-nitro-G-methylanthraquinone,and 1- (2 thenoylamino) 2,4 dibromo 5 nitro-G- methylanthraquinone.

Thenoylaminoanthraquinone compounds are preferably prepared bycondensation of aminoanthraquinones with reactive compounds of 2-thenoic acid and its derivatives, such as the acid chlorides and theanhydrides. Where reactive groups are present in the molecule, theproducts can then be further reacted. The reactions may be carried outin inert organic solvents such as nitrobenzene, the chlorinated benzenesand the aromatic hydrocarbons. The reaction conditions may be variedwidely with respect to time and temperature, depending on the particularreactants employed. A temperature range of 110 to 175C. usually givessatisfactory results in the thenoylation of aminoanthraquinones, while arange of 140 to 205 C. is generally suitable forfurther reactions of thethenOylaminoanthraquinones although conditions outside of these rangesmay, of course, be employed where found desirable. The time of reactiondepends upon the temperature chosen and the reactants used. For thethenoylation reaction, catalysts may be used, and in the furthercondensation of otherwise substituted thenoylaminoanthraquinones withother compounds, the usual catalysts such as copper salts, and acidbinders such as inorganic or organic basic salts, may be employed.

Thenoylamino derivatives of anthraquinone compounds are valuableintermediates for dyes and for certain fibers they are dyes inthemselves. The new compounds of this invention are particularly usefulin that they are generallydeeper in shade than thebenzoylaminoanthraquinones, showing increased molecular color value, andgive dyes of desirable shades and properties not previously attainable.The unusual and unexpected effect of the thenoylamino group on the colorproperties of even the simplest anthraquinone derivative is wellillustrated by a comparison of l-amino-ibenzoylaminoanthraquinone with1-amino-4-(2- thenoylamino) anthraquinone. When compared in the GeneralElectric Spectrophotometer, the thenoylamino compound is 38.7% strongeron'an equal weight basis and 39.3 stronger on a molecular basis.Furthermore, there is a very pronounced bathochromic efiect produced bythe thenoyl group present in the new molecule.

We claim:

1. Thenoylaminoanthraquinone compounds of the general formula:

[.llml

in which'n stands for one of the numbers 1 and 2 and Aq stands for ananthraquinone nucleus of thegroup consisting of the otherwiseunsubstituted anthraquinone nucleus and the anthraquinone nuclei whichcarry not more than three 'substituents of the group consisting ofC1,Br,

3. l- (2-thenoylamino) 5-chloroanthraquinone.

4=. l- (5-chloro-2-thenoylamino) 4-methoxy-5- chloroanthraquinone.

5. '1- (5-chloro- 2 thenoylamino) 5 -chloroantraquinone.

' HENRY R. LEE.

CLARENCE F. BELCHER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS I Date Number Name 2,144,220 Etzelmiller Jan. 17,1939 Murray Mar. 24, 1942 OTHER. REFERENCES Houben, "Das Anthracen unddie Anthrachinone, p. 419, Thieme, Liepzig, 1929.

Richter, Organic Chemistry, pp. 649-50, John Wiley, N. Y., 1938.

1. THENOYLAMINOANTHRAQUINONE COMPOUNDS OF THE GENERAL FORMULA: